CN100409943C - Method for preparing nano noble metal hydrogenation catalyst by substitution method and its use - Google Patents
Method for preparing nano noble metal hydrogenation catalyst by substitution method and its use Download PDFInfo
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- CN100409943C CN100409943C CNB2005102004351A CN200510200435A CN100409943C CN 100409943 C CN100409943 C CN 100409943C CN B2005102004351 A CNB2005102004351 A CN B2005102004351A CN 200510200435 A CN200510200435 A CN 200510200435A CN 100409943 C CN100409943 C CN 100409943C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 56
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 56
- 238000006467 substitution reaction Methods 0.000 title claims description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000000126 substance Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 239000000084 colloidal system Substances 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims description 35
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
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- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
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- TZIHFWKZFHZASV-UHFFFAOYSA-N anhydrous methyl formate Natural products COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical group OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 13
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- 125000003118 aryl group Chemical group 0.000 abstract description 2
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- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 abstract 1
- 150000001336 alkenes Chemical class 0.000 abstract 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 150000001728 carbonyl compounds Chemical class 0.000 abstract 1
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- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
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- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 150000007984 tetrahydrofuranes Chemical class 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- CFBYEGUGFPZCNF-UHFFFAOYSA-N 2-nitroanisole Chemical compound COC1=CC=CC=C1[N+]([O-])=O CFBYEGUGFPZCNF-UHFFFAOYSA-N 0.000 description 3
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- SJWQCBCAGCEWCV-UHFFFAOYSA-N n-(3-amino-4-methoxyphenyl)acetamide Chemical compound COC1=CC=C(NC(C)=O)C=C1N SJWQCBCAGCEWCV-UHFFFAOYSA-N 0.000 description 3
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 3
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 3
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 2
- KSMVBYPXNKCPAJ-UHFFFAOYSA-N 4-Methylcyclohexylamine Chemical compound CC1CCC(N)CC1 KSMVBYPXNKCPAJ-UHFFFAOYSA-N 0.000 description 2
- IMPPGHMHELILKG-UHFFFAOYSA-N 4-ethoxyaniline Chemical compound CCOC1=CC=C(N)C=C1 IMPPGHMHELILKG-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
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- POTIYWUALSJREP-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydroquinoline Chemical compound N1CCCC2CCCCC21 POTIYWUALSJREP-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- OUXLUHHXKDPSOZ-UHFFFAOYSA-N 4-(4-propylphenyl)phenol Chemical compound C1=CC(CCC)=CC=C1C1=CC=C(O)C=C1 OUXLUHHXKDPSOZ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
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- YECIFGHRMFEPJK-UHFFFAOYSA-N lidocaine hydrochloride monohydrate Chemical compound O.[Cl-].CC[NH+](CC)CC(=O)NC1=C(C)C=CC=C1C YECIFGHRMFEPJK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a method for preparing nanometer noble metal hydrogenation catalyst by using chemical replacement processes and application thereof, which belongs to the field of the preparation and application technique of a hydrogenation catalyst with high activity. Metal simple substances M and the salt of noble metals N are utilized to generate simple substances N through replacement reaction, wherein N represents Ru, Rh, Pd, Pt, Ir or mixtures thereof and M represents Zn, Al, Fe, Co and Ni. When M is terrifically excess, a nanometer noble metal with N/M type metals load is generated; when N and M are approximate to stoichiometry, a highly-dispersed nanometer N colloid is generated; when a stabilizing agent is added, a load type N/S is prepared, wherein S represents C, Al2O3, SiO2, MgO, ZrO2 and CeO2. Having the advantages of simple and direct catalyst preparation technology, and easy regeneration, the present invention is suitable for hydrogenation reaction for alkene, acetylene hydrocarbon, aromatic substances, nitro compounds, nitrile base compounds, esters, carboxylic acids, aldehydes, ketones, carbonyl compounds, etc.
Description
Technical field
The invention belongs to the preparation and the applied technical field of high-activity hydrogenation catalyst, relate to the salt that utilizes metal simple-substance M and noble metal N,, generate simple substance N by displacement reaction.Wherein N represents Ru, Rh, Pd, Pt, Ir or its mixture, and M represents Zn, Al, Fe, Co, Ni.When M is very big when excessive, generate the nano-noble metal of N/M type metal load; As N and M during near stoichiometry, generate the nanometer N colloid of high degree of dispersion, add stabilizing agent after, can prepare support type N/S, wherein S represents C, Al
2O
3, SiO
2, MgO, ZrO
2, CeO
2
Background technology
Catalytic hydrogenation is one of modal reaction in the Chemical Manufacture, and noble metal catalyst is again one of the most frequently used hydrogenation catalyst.Noble metal catalyst commonly used in the heterogeneous hydrogenation is a support type, such as Pd/C, Pd/Al
2O
3, Ru/C, Ru/SiO
2, Pt/C, RhRu/Al
2O
3, be worldwide hot subject for many years to loaded noble metal catalyst preparation method, improvement in performance and new research of using always, constantly there are a large amount of articles and patent to deliver.Although it has been found that the noble metal hydrogenation catalyst of many excellent performances so far and obtained extensive use industrial, but because noble metal costs an arm and a leg, people wait in expectation always and develop the noble metal catalyst that load capacity is lower, activity is higher, the life-span is longer.Be in order to reduce the needed high-temperature and high-pressure conditions of hydrogenation reaction such as industrial common aromatic ring, ester group, carboxyl, to reduce energy consumption and avoid using harsh high-tension apparatus on the one hand; Be in order to adapt to of the tight demand of modern field of fine chemical on the other hand to low-temperature catalyzed hydrogenation reaction.Because the preparation of high added value intermediates such as many in recent years liquid crystal, polyurethane and medicine all relates to hydrogenation reduction, and the reaction temperature of existing hydrogenation catalyst and pressure are higher than the requirement of these special reduction reactions, cause poor selectivity, yield is low, so have to use costliness and to the disagreeableness traditional chemical reduction method of environment
So far, one of main direction of studying of noble metal catalyst is the decentralization that increases noble metal granule, makes it have nano-scale.Around this direction, people have carried out number of research projects, have emerged many new methods, such as: LiAlH
4, NaBH
4, N
2H
4Room temperature electronation load method; Metal organic chemical compound vapor deposition method (MOCVD); Electrochemical deposition method; Photoreduction met hod or the like.These methods respectively have advantage, but its common shortcoming is that preparation process is loaded down with trivial details, the cost costliness.
By the chemical replacement reaction of cheap metal simple substance and noble metal inorganic salts, the preparation nano noble metal hydrogenation catalyst is a brand-new method, does not see any bibliographical information as yet.The load capacity of noble metal can be very low, and in the carrier surface high degree of dispersion, such catalyst has very high hydrogenation activity, can be under room temperature and normal pressure or several pressure, and the hydrogenation reaction of the multiple unsaturated bond of catalysis.Therefore, this important function for of research has important practical sense and using value.
Summary of the invention
Purpose of the present invention is utilized chemical replacement method principle exactly, provide that a kind of preparation method is simple and easy, manufacturing cycle is short, noble metal dosage is low, cost is low, than the preparation method of the nano noble metal hydrogenation catalyst of hydrogenation activity height, reaction condition gentleness, with and application in unsaturated organo-functional group hydrogenation reaction.
Principle of the present invention is, is dissolved in noble metal N salt or complex compound in the solvent, with active metal M particulate generation chemical replacement reaction, generates nano level precious metal simple substance N under stirring condition.When M is very big when excessive, N loads on excessive metal particle surface, becomes the nano-noble metal catalyst of metal load, although the specific area of metal particle is very little, because load capacity can be very low, so the specific activity of catalyst is very high; When the consumption of M during near stoichiometry, generate the nanometer N colloid of high degree of dispersion, add stabilizing agent after, can be used for preparing common support type N/S hydrogenation catalyst.
Technical solution of the present invention is, effectively controls the chemical replacement course of reaction, and the precious metal simple substance N that makes generation is the nano particle of high degree of dispersion.
A kind of method of preparing nano noble metal hydrogenation catalyst by substitution method is with the salt of metal simple-substance M and noble metal N, at temperature 20-150 ℃, pressure 1Kg/cm
2(normal pressure)-15Kg/cm
2Under the condition, in solvent, carry out the chemical replacement reaction, generate the precious metal simple substance N of nanometer particle size, reaction time is from 3 minutes to 2 hours, the particle diameter of used metal simple-substance M is 5 nanometers-500 micron, the mol ratio of N and M is 1: 1-1: 10000, and the consumption of solvent is M and N gross weight 1-100 a times, wherein:
N is selected from least a among Ru, Rh, Pd, Pt, the Ir;
M is selected from least a among Zn, Al, Fe, Co, the Ni;
Solvent is selected from least a in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, propane diols, isopropyl alcohol, water, acetone, MEK, oxolane, dioxane, methyl ether, ether, ethyl methyl ether, methyl formate, Ethyl formate, ethyl acetate and the methyl acetate, and the purity of solvent is chemical reagent-grade.
When the consumption of M surpassed the metering of chemical reaction, promptly the mol ratio as N and M was 1: 10-1: in the time of 10000, and normally 1: 100-1: 300 o'clock, the nano-noble metal of generation N/M type metal load.
When the mol ratio of N/M equals or during near the stoichiometry of chemical replacement reaction, promptly the mol ratio as N and M is 1: 1-1: in the time of 10, normally 1: 2-1: 4 o'clock, the nano-noble metal N colloid of generation high degree of dispersion.
In the chemical replacement course of reaction, perhaps when reaction has just finished, in nano-noble metal N colloidal solution, add stabilizing agent R, the loaded nano noble metal hydrogenation catalyst N/S that preparation is conventional, by weight percentage, the load capacity of N is 0.1-20%, and wherein 0.3wt%-5wt% is ideal; Used stabilizing agent R is selected from ethylene glycol, diethylene glycol (DEG), triethylene glycol, 1, ammediol, 1, at least a in 4-butanediol and the C5-C18 fatty alcohol; Wherein:
S is selected from C, Al
2O
3, SiO
2, MgO, ZrO
2, CeO
2In at least a.
This chemical replacement reaction response carries out between the 30-60 degree usually.
This chemical replacement reaction response is usually at normal pressure-3Kg/cm
2Between carry out.
This chemical replacement reaction response time was the best with 30-60 minute.
The particle diameter of the metal M that this chemical replacement reaction is used is micron the most commonly used in 20 nanometers-1.
This chemical replacement reaction is carried out in glass beaker usually.
Carry out in the gram bottle of Shulan, make blanketing with inert gas.
Carry out in the still formula pressure reactor, make blanketing with inert gas.
React prepared nano-noble metal with chemical replacement and be of a size of 1 nanometer, wherein 2 nanometers the most important between 10 nanometers to 100 nanometers; The structural form of catalyst is that the nano-noble metal particulate load is on metal M or carrier S surface.
Use a kind of method of preparing nano noble metal hydrogenation catalyst by substitution method, this catalyst is applicable to the hydrogenation reaction of polyurethane monomer M DA, preparation H
12MDA, reaction temperature is the 50-150 degree, pressure is 10-50Kgcm
-2, solvent is a kind of or its mixture in the tetrahydrochysene furan food in one's mouth, dioxane, the decahydronaphthalene, the ratio of solvent and reactant is 1: 1-1: and 10, catalyst amount is the 3-15wt% of reactant liquor; Reaction time 1-4 hour, the MDA conversion ratio was 100%, product H
12The content of transisomer is usually less than 20% among the MDA, minimumly can reach 8%.
Use a kind of method of preparing nano noble metal hydrogenation catalyst by substitution method, this catalyst is applicable to the hydrogenation preparing 4-alkyl cyclohexanol of 4-alkylphenol, it is characterized in that, reaction temperature is the 50-150 degree, compressive force 5-30Kgcm
-2, solvent is oxolane, dioxane or its mixture, the ratio of solvent and reactant is 1: 1-1: 10, catalyst amount is the 1-15wt% of reactant liquor, reaction time 0.5-4 hour, the yield of product 4-alkyl cyclohexanol was up to 100% usually above 97%.
Use a kind of method of preparing nano noble metal hydrogenation catalyst by substitution method, this catalyst is applicable to hydrogenation preparing liquid crystal monomer 4-(the 4-n-pro-pyl cyclohexyl) cyclohexanol of 4-(4-n-pro-pyl phenyl) phenol, it is characterized in that reaction temperature is the 50-150 degree, pressure is 5-30Kgcm
-2Solvent is oxolane, dioxane or its mixture, the ratio of solvent and reactant is 1: 1-1: 10, catalyst amount is the 1-15wt% of reactant liquor, reaction time 0.5-4 hour, the yield of product 4-(4-n-pro-pyl cyclohexyl) cyclohexanol is usually above 96%, the highlyest can reach 100%.
Use a kind of method of preparing nano noble metal hydrogenation catalyst by substitution method, this catalyst is applicable to the benzoic hydrogenation preparing liquid crystal monomer 4-of 4-(4-n-pro-pyl cyclohexyl) (4-n-pro-pyl cyclohexyl) hexahydrobenzoid acid, it is characterized in that, reaction temperature is the 60-150 degree, and pressure is 10-30Kgcm
-2Solvent is oxolane, dioxane or its mixture, the proportional force 1 of solvent and reactant: 1-1: 10, catalyst amount is the 1-15wt% of reactant liquor, reaction time 0.5-4 hour, the yield of product 4-(4 n-pro-pyl cyclohexyl) hexahydrobenzoid acid is usually above 97%, the highlyest can reach 100%.
Use a kind of method of preparing nano noble metal hydrogenation catalyst by substitution method, this catalyst is applicable to that phenol hydrogenation prepares cyclohexanol, it is characterized in that, and reaction temperature 70-110 ℃, Hydrogen Vapor Pressure 10-25Kgcm
-2, catalyst amount is the 1-15wt% of reactant liquor, without solvent, reacts after 1-2 hour, phenol 100% is converted into cyclohexanol.
Use a kind of method of preparing nano noble metal hydrogenation catalyst by substitution method, this catalyst is applicable to the quinoline hydrogenation, it is characterized in that, reaction temperature is the 60-150 degree, and pressure is 10-30Kgcm
-2This reaction can be without solvent, also can select oxolane, dioxane, decahydronaphthalene or its mixture is solvent, the ratio of solvent and reactant is 1: 10-10: 1, catalyst amount is the 1-15wt% of reactant liquor, reaction time 0.5-4 hour, the yield of product decahydroquinoline was usually greater than 99%, the highlyest can reach 100%.
Use a kind of method of preparing nano noble metal hydrogenation catalyst by substitution method, this catalyst is applicable to that the reduction of 3-nitro-4-p-methoxyacetanilide prepares dyestuff intermediate 3-amino-4-methoxyacetanilide, it is characterized in that reaction temperature is the 30-120 degree, pressure is 5-20Kgcm
-2This reaction is a solvent with oxolane, dioxane or its mixture, the ratio of solvent and reactant is 1: 10-10: 1, catalyst amount is the 1-15wt% of reactant liquor, reaction time 0.5-4 hour, the yield of corresponding target product 3-amino-4-methoxyacetanilide is greater than 99%, the highlyest can reach 100%.
Use a kind of method of preparing nano noble metal hydrogenation catalyst by substitution method, this catalyst is applicable to the hydrogenation preparing paraphenetidine of paranitroanisole, it is characterized in that, reaction temperature is the 30-120 degree, and pressure is 2-20Kgcm
-2This reaction is a solvent with oxolane, dioxane or its mixture, the ratio of solvent and reactant is 1: 10-10: 1, catalyst amount is the 1-15wt% of reactant liquor, reaction time 0.5-4 hour, the yield of purpose product paraphenetidine is usually greater than 99%, the highlyest can reach 100%.
Use a kind of method of preparing nano noble metal hydrogenation catalyst by substitution method, this catalyst is applicable to the corresponding amino-chloro-benzene compound of the hydrogenation preparing of paranitrochlorobenzene and o-nitrochlorobenzene, it is characterized in that reaction temperature is the 30-120 degree, pressure is 2-20Kgcm
-2This reaction is a solvent with oxolane, dioxane or its mixture, the ratio of solvent and reactant is 1: 10-10: 1, catalyst amount is the 1-15wt% of reactant liquor, reaction time 0.5-4 hour, the yield of corresponding target product amino-chloro-benzene is usually greater than 99%, the highlyest can reach 100%, do not have tangible dechlorination side reaction, selectivity height.
Use a kind of method of preparing nano noble metal hydrogenation catalyst by substitution method, this catalyst is applicable to the corresponding 1-methyl of the hydrogenation preparing of methylaniline-4-aminocyclohexane.It is characterized in that reaction temperature is the 60-110 degree, pressure is 5-15Kgcm
-2This reaction is a solvent with oxolane, dioxane or its mixture, the ratio of solvent and reactant is 1: 10-10: 1, catalyst amount is the 1-15wt% of reactant liquor, reaction time 0.5-2.5 hour, the yield of corresponding target product 1-methyl-4-aminocyclohexane reached 100% usually.
Use a kind of method of preparing nano noble metal hydrogenation catalyst by substitution method, this catalyst is applicable to that the hydrogenation preparing of p-methyl phenol is to methyl cyclohexanol. it is characterized in that reaction temperature is the 50-100 degree, pressure is 5-20Kgcm
-2This reaction is a solvent with oxolane, dioxane or its mixture, and the ratio of solvent and reactant is 1: 10-10: 1, and catalyst amount is the 1-15wt% of reactant liquor, reaction time 0.5-2.5 hour, the corresponding target product reached 100% usually to the yield of methyl cyclohexanol.
Use a kind of method of preparing nano noble metal hydrogenation catalyst by substitution method, this catalyst is applicable to the hydrogenation preparing P-nethoxyaniline of methoxy nitrobenzene.It is characterized in that reaction temperature is the 50-100 degree, pressure is 5-20Kgcm
-2This reaction is a solvent with oxolane, dioxane or its mixture, the ratio of solvent and reactant is 1: 10-10: 1, catalyst amount is the 1-15wt% of reactant liquor, reaction time 0.5-2 hour, the corresponding target product reaches 99% usually to the yield of P-nethoxyaniline, can reach 100%.
The beneficial effect that the present invention reached is, this catalyst presents remarkable activity for the catalytic hydrogenation reaction of multiple unsaturated organo-functional group under low-temp low-pressure, the side reaction that can effectively suppress high-temperature hydrogenation and brought; To the hydrogenation reaction that has multiple isomers to generate, obviously improve the yield of the isomers of low-temperature stabilization.This catalyst preparation technology is simple and direct, and regeneration has favorable industrial application prospect and huge market potential easily.
Description of drawings
The present invention is further illustrated below in conjunction with the drawings and specific embodiments.
Fig. 1 is the transmission electron microscope picture of the Ru particulate load of 2 nanometers that prepare of the present invention on metal A l surface.
The specific embodiment
Embodiment 1
Ru/Al Preparation of catalysts example:
Related Preparation of catalysts method among the present invention, with aluminium load factor nanometer ruthenium is that exemplary is illustrated: per 0.1 gram ruthenium salt is dissolved in the 20-100 milliliter solvent in autoclave, it with particle diameter 20500 microns metal simple-substance M powder, with mol ratio 1: 30-1: 2000 ratio adds in the autoclave, fill the inert nitrogen gas displacement under the normal temperature, under room temperature to 150 ℃ condition, stir more than 30 minutes cessation reaction, open the still inspection, at this moment RuCl in the solution
3Characteristic color decorporate fully.According to the difference of consumption, the surface color overstrike or the black of Al particulate.Nitrogen protection is filtered down, uses the solvent cyclic washing, and drying promptly gets the nano-ruthenium catalyst of metallic aluminium load.
Embodiment 2
In 70 milliliters of autoclaves, add 0.1 gram hydrate ruthenium trichloride solid, the 20-60 ml deionized water, with particle diameter is the metal nickel powder of 20-500 micron, and with mol ratio 1: 50-1: 2000 ratio adds in the autoclave, fill inert nitrogen gas displacement air under the normal temperature after, be stamped into 0.5MPa, heat temperature raising starts stirring to 50-80 ℃, reacted 1 hour, be cooled to room temperature, drive still, use deionized water, solid in the repeated multiple times washing still promptly makes the Ni nano-ruthenium catalyst.
Get the 2 gram catalyst that the step makes, place autoclave, adds 20 milliliters of benzene, the envelope still, lead to hydrogen exchange after,, add to hold and be warming up to 60 ℃ to 1.0MPa towards Hydrogen Vapor Pressure, start stirring, reacted 1 hour, gas chromatographic analysis, benzene 100% changes into cyclohexane.
Embodiment 3
In 70 milliliters of autoclaves, add 0.1 gram hydrate ruthenium trichloride solid, the 20-60 ml deionized water, with particle diameter is the metal iron powder of 20-500 micron, and with mol ratio 1: 50-1: 2000 ratio adds in the autoclave, under the normal temperature after the inflated with nitrogen displaced air, be stamped into 0.5MPa, heat temperature raising starts stirring to 30-80 ℃, reacts 1 hour, be cooled to room temperature, drive still,, promptly make iron loaded with nano ruthenium catalyst with solid in the deionized water repeated multiple times Xian Di still.
Get the step make about 2 the gram catalyst place autoclave, add 20 milliliters of acetone, other condition is with embodiment 2, acetone 100% is converted into isopropyl alcohol.
Embodiment 4
In 100 milliliters of autoclaves, add 0.1 gram hydration tri-chlorination nail solid, 40 milliliters of acetone are the metal zinc of 20-500 micron with particle diameter, and with mol ratio 1: 50-1: 2000 ratio adds in the autoclave, under the normal temperature after the inflated with nitrogen displaced air, heat temperature raising after 40 minutes, stops reaction to 30-60 ℃, with solid in the acetone repeated multiple times Xian Di still, make zinc loaded with nano ruthenium catalyst.
Get the step make about 2 the gram catalyst place autoclave, add 20 milliliters of phenol, 90 ℃ of reaction temperatures, Hydrogen Vapor Pressure 2.0MPa reacted after 2 hours, sample analysis, phenol 100% is converted into cyclohexanol.
Embodiment 5
In 100 milliliters of autoclaves, add 0.1 gram hydrate ruthenium trichloride solid, 40 milliliters of acetone are the metallic aluminium powder of 20-500 micron with particle diameter, and with mol ratio 1: 50-1: 2000 ratio adds in the autoclave, under the normal temperature after the inflated with nitrogen displaced air, heat temperature raising after 20-40 minute, stops reaction to 30-60 ℃, with solid in the acetone repeated multiple times Xian Di still, make aluminium loaded with nano ruthenium catalyst.
Get the step make about 1 the gram catalyst place autoclave, adding 20 milliliters of tetrahydrochysene furans feeds, 5 gram parachloronitrobenzenes, 85 ℃ of reaction temperatures, reacted 2 hours, Hydrogen Vapor Pressure 1.0MPa, other condition is with embodiment 2, reaction result. chlorine substituent there is no to be sloughed, and parachloronitrobenzene 100% is converted into parachloroanilinum.
Embodiment 6
Get catalyst 1 gram that makes among the embodiment 4, place autoclave, add 20 milliliters of oxolanes, 5 grams are to methylaniline, and 90 ℃ of reaction temperatures were reacted 2.5 hours, Hydrogen Vapor Pressure 1.0MPa, other condition is converted into 1-methyl-4-aminocyclohexane with embodiment 2 to methylaniline 100%.
Embodiment 7
Get catalyst 1 gram that makes among the embodiment 4, place autoclave, add 20 milliliters of oxolanes, 5 gram p-methyl phenols, 60 ℃ of reaction temperatures were reacted 2.5 hours, Hydrogen Vapor Pressure 2.0MPa, other condition is with embodiment 2, and p-methyl phenol 100% is converted into methyl cyclohexanol, and the cis-trans-isomer ratio is 80: 20 in the product.
Embodiment 8
Get catalyst 1.5 grams that make among the embodiment 4, place autoclave, add 20 milliliters of oxolanes, 3 gram 3-nitro-4-p-methoxyacetanilides, 70 ℃ of reaction temperatures were reacted 2.5 hours, Hydrogen Vapor Pressure 1.7MPa, other condition is with embodiment 2, and reaction result: nitro is reduced into amino by selectivity, and 3-nitro-4-p-methoxyacetanilide 100% is converted into the 3-amino-4-methoxyacetanilide.
Embodiment 9
Get catalyst 1.5 grams that make among the embodiment 4, place autoclave, add 20 milliliters of oxolanes, 5 grams are to methoxy nitrobenzene, 75 ℃ of reaction temperatures were reacted Hydrogen Vapor Pressure 1.5MPa 1.5 hours, other condition is with embodiment 2, reaction result: methoxy nitrobenzene 100% is converted into P-nethoxyaniline.
Claims (9)
1. the method for a preparing nano noble metal hydrogenation catalyst by substitution method is characterized in that, with the salt of metal simple-substance M and noble metal N, at temperature 20-150 ℃, pressure 1-15kg/cm
2Under the condition, in solvent, carry out the chemical replacement reaction, generate the precious metal simple substance N of nanometer particle size, reaction time is from 3 minutes to 2 hours, the particle diameter of used metal simple-substance M is 5 nanometers-500 micron, the mol ratio of N and M is 1: 1-1: 10000, and the consumption of solvent is M and N gross weight 1-100 a times; Wherein:
N is selected from least a among Ru, Rh, Pd, Pt, the Ir;
M is selected from least a among Zn, Al, Fe, Co, the Nl;
Solvent is selected from least a in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, propane diols, isopropyl alcohol, water, acetone, MEK, oxolane, dioxane, methyl ether, ether, ethyl methyl ether, methyl formate, Ethyl formate, ethyl acetate and the methyl acetate, and the purity of solvent is chemical reagent-grade.
2. the method for a kind of preparing nano noble metal hydrogenation catalyst by substitution method according to claim 1 is characterized in that, when the mol ratio of N and M is 1: 10-1: in the time of 10000, generate the nano-noble metal of N/M type metal load.
3. the method for a kind of preparing nano noble metal hydrogenation catalyst by substitution method according to claim 1 is characterized in that, when the mol ratio of N and M is 1: 1-1: in the time of 10, generate the nano-noble metal N colloid of high degree of dispersion
4. the method for a kind of preparing nano noble metal hydrogenation catalyst by substitution method according to claim 3, it is characterized in that, in nano-noble metal N colloidal solution, add stabilizing agent R, the loaded nano noble metal hydrogenation catalyst N/S that preparation is conventional, by weight percentage, the load capacity of N is 0.1-20%; Used stabilizing agent R is selected from ethylene glycol, diethylene glycol (DEG), triethylene glycol, 1, ammediol, 1, at least a in 4-butanediol and the C5-C18 fatty alcohol, its consumption be the N that generated molal quantity 1-100 doubly; Wherein:
S is selected from C, Al
2O
3, S
1O
2, MgO, ZrO
2, CeO
2In at least a.
5. the method for a kind of preparing nano noble metal hydrogenation catalyst by substitution method according to claim 1 is characterized in that, this chemical replacement reaction response time is 30-60 minute.
6. the method for a kind of preparing nano noble metal hydrogenation catalyst by substitution method according to claim 1 is characterized in that, the particle diameter of the metal M that this chemical replacement reaction is used is 20 nanometers-1 micron.
7. the method for a kind of preparing nano noble metal hydrogenation catalyst by substitution method according to claim 1 is characterized in that, this chemical replacement reaction is carried out in glass beaker usually.
8. the method for a kind of preparing nano noble metal hydrogenation catalyst by substitution method according to claim 1 is characterized in that, carries out in the gram bottle of Shulan, makes blanketing with inert gas.
9. the method for a kind of preparing nano noble metal hydrogenation catalyst by substitution method according to claim 1 is characterized in that, carries out in the still formula pressure reactor, makes blanketing with inert gas.
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| CN100428989C (en) * | 2006-09-06 | 2008-10-29 | 大连理工大学 | Method for preparing loading type nano Pd/C catalyst from colloidal solution |
| CN101347843B (en) * | 2008-09-12 | 2011-06-08 | 安徽工业大学 | Method for preparing metallic nickel nano powder |
| CN101817088B (en) * | 2009-02-27 | 2011-12-28 | 天津商业大学 | Preparation method of Pt-Ni alloy nano particle and colloidal dispersion system thereof |
| CN104190417B (en) * | 2014-07-21 | 2017-01-25 | 复旦大学 | Preparation method of ruthenium-based bimetallic catalyst for preparing cyclohexene by partial hydrogenation of benzene |
| CN105521797B (en) * | 2014-09-28 | 2018-02-23 | 中国石油化工股份有限公司 | Load type double-metal component catalyst and preparation method and application and aromatic saturated hydrogenation method |
| CN104857973B (en) * | 2015-04-28 | 2017-04-05 | 华南理工大学 | A kind of loaded catalyst with core shell structure and preparation method and application |
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| CN108067238B (en) * | 2018-01-14 | 2020-10-09 | 常州大学 | Metallic cobalt catalyst for catalyzing o-methoxyphenol to prepare cyclohexanol and preparation method thereof |
| CN108579794A (en) * | 2018-04-02 | 2018-09-28 | 新疆大学 | The molecular sieve catalyst of gold-supported is used to convert the method that methanol is methyl acetate |
| CN110339844B (en) * | 2018-04-08 | 2021-08-17 | 中国科学院大连化学物理研究所 | Fe nanorod and Pt @ Fe nanorod catalyst as well as synthesis and application thereof |
| CN109585843B (en) * | 2018-11-12 | 2021-09-21 | 昆明理工大学 | Preparation method of high-nickel ternary nickel-cobalt-aluminum positive electrode material precursor |
| CN116115818B (en) * | 2021-11-12 | 2024-06-28 | 重庆百迈腾世医药科技有限公司 | Active metal microsphere, composite embolic agent based on active metal microsphere and application of composite embolic agent |
| CN115555017B (en) * | 2022-10-17 | 2024-04-05 | 中化泉州能源科技有限责任公司 | Dechlorination type carbon five petroleum resin hydrogenation catalyst and preparation method thereof |
| CN116116442B (en) * | 2023-02-20 | 2023-12-22 | 常州大学 | Preparation method and application of low-load sub-nanometer noble metal catalyst |
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